U.S. patent number 10,093,690 [Application Number 15/370,472] was granted by the patent office on 2018-10-09 for heterocyclic selenaphosphites and process for preparation thereof.
This patent grant is currently assigned to EVONIK DEGUSSA GMBH. The grantee listed for this patent is EVONIK DEGUSSA GMBH. Invention is credited to Armin Borner, Katrin Marie Dyballa, Robert Franke, Detlef Selent, Claudia Weilbeer.
United States Patent |
10,093,690 |
Dyballa , et al. |
October 9, 2018 |
Heterocyclic selenaphosphites and process for preparation
thereof
Abstract
Novel heterocyclic selenaphosphites, process for preparation
thereof and use thereof as ligand for employment in complexes.
Inventors: |
Dyballa; Katrin Marie
(Recklinghausen, DE), Franke; Robert (Marl,
DE), Weilbeer; Claudia (Bernburg, DE),
Selent; Detlef (Rostock, DE), Borner; Armin
(Rostock, DE) |
Applicant: |
Name |
City |
State |
Country |
Type |
EVONIK DEGUSSA GMBH |
Essen |
N/A |
DE |
|
|
Assignee: |
EVONIK DEGUSSA GMBH (Essen,
DE)
|
Family
ID: |
54834682 |
Appl.
No.: |
15/370,472 |
Filed: |
December 6, 2016 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20170158721 A1 |
Jun 8, 2017 |
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Foreign Application Priority Data
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Dec 7, 2015 [EP] |
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15198153 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C
37/00 (20130101); C07C 29/00 (20130101); C07F
9/65744 (20130101); C07F 9/547 (20130101) |
Current International
Class: |
C07F
9/547 (20060101); C07C 29/00 (20060101); C07C
37/00 (20060101); C07F 9/6574 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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102013203865 |
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Sep 2014 |
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DE |
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102013203867 |
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Sep 2014 |
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DE |
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2949646 |
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Dec 2015 |
|
EP |
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Other References
Chemical Abstract Registry No. 859821-79-7, indexed in the Registry
File on STN CAS Online Aug. 12. 2005. cited by examiner .
International Search Report for EP 15 19 8153 dated May 19, 2016 (1
page). cited by applicant .
Li, J. L. et al. Synthesis of phosphorus- and selenium-containing
macrocycles and their complexation with Pd (II) Cl2. Journal of The
Chemical Society, Perkin Transactions 1, (9), 2001, 1140-1146.
cited by applicant .
Franke, R., Selent, D., and Borner, A. Applied Hydroformylation.
American Chemical Society, ACS Publications, Chemical Reviews,
2012. 5675-5732. cited by applicant .
Tricas, Hugo, et, al, Bulky monophosphite ligands for ethene
hydroformylation, J. of Catalysis, 2012, 198-205. cited by
applicant .
Paine, Tapan Kanti, et al. Manganese complexes of mixed O, X, O
CHEN, -donor ligands (X=S or Se): synthesis, characterization and
catalytic reactivity. Dalton Trans. 2003, 3136-3144. cited by
applicant .
Kamer, Paul C. J. et. al. Phosphorus (III) Ligands in Homogeneous
Catalysis: Design and Synthesis. John Wiley and Sons, LTD. 2012,
94-131. cited by applicant .
Lin, He M., et. al. A novel and efficient synthesis of selenides.
Arkivoc, 2012, 146-156. cited by applicant.
|
Primary Examiner: Chen; Po-Chih
Attorney, Agent or Firm: Smith, Gambrell & Russell,
LLP
Claims
The invention claimed is:
1. A heterocyclic selenaphosphite compound having a general
structure (I) ##STR00017## where R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each
independently selected from: --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.6-C.sub.20-aryl, -halogen,
--OC.dbd.O--(C.sub.1-C.sub.12)-alkyl, --S-alkyl,--S-aryl,
--COO--(C.sub.1-C.sub.12)-alkyl, --CONH--(C.sub.1-C.sub.12)-alkyl,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --SO.sub.3H, --CN, or --N[(C.sub.1-C.sub.12)-alkyl].sub.2,
where the alkyl groups are each independently linear, branched or
cyclic, where the alkyl and aryl groups are each independently
unsubstituted or substituted, where each substituted
--(C.sub.1-C.sub.12)-alkyl group and substituted
--(C.sub.6-C.sub.20)-aryl group has at least one substituent and
the at least one substituent in each case is independently selected
from --(C.sub.3-C.sub.12)-cycloalkyl,
--(C.sub.3-C.sub.12)-heterocycloalkyl, --(C.sub.6-C.sub.20)-aryl,
fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, and
where --R.sup.1 is independently selected from
--O--(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.6-C.sub.20)-aryl-O--(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, or
--O--(C.sub.3-C.sub.12)-cycloalkyl, where the alkyl groups are
linear, branched or cyclic, Where the alkyl and aryl groups
mentioned are each independently unsubstituted or substituted, each
substituted --(C.sub.6-C.sub.20)-aryl group has at least one or
more than one substituent, and where the substituents on each aryl
group are independently selected from:
--O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.1-C.sub.12-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.3-C.sub.12)-cycloalkyl,
--(C.sub.3-C.sub.12)-heterocycloalkyl, --(C.sub.6-C.sub.20)-aryl,
cyano, -halogen, --OCOO--(C.sub.1-C.sub.12)-alkyl, or
--N[(C.sub.1-C.sub.12)-alkyl].sub.2.
2. The compound according to claim 1, wherein in the heterocyclic
selenaphosphite of the general structure (I), R.sup.1 is selected
from the structures (II), (III), (IV), (V), (VI), (VII), (VIII),
(IX) and (X) ##STR00018## ##STR00019## where the radicals R.sup.10,
R.sup.11, R.sup.12, R.sup.13, R.sup.14 in the structure (II),
R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20,
R.sup.21, R.sup.22 and R.sup.23 in structure (III), R.sup.24,
R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30,
R.sup.31, R.sup.32, R.sup.33 and R.sup.34 in structure (IV),
R.sup.35, R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40,
R.sup.41, R.sup.42, R.sup.43, R.sup.44 and R.sup.45 in structure
(V), R.sup.46, R.sup.47, R.sup.48, R.sup.49, R.sup.50, R.sup.51,
R.sup.52, R.sup.53, R.sup.54, R.sup.55, R.sup.56, R.sup.57 and
R.sup.58 in structure (VI), R.sup.59, R.sup.60, R.sup.61, R.sup.62,
R.sup.63, R.sup.64 and R.sup.65 in structure (VII), and R.sup.66,
R.sup.67, R.sup.68, R.sup.69, R.sup.70, R.sup.71, R.sup.72,
R.sup.73 and R.sup.74 in structure (VIII), in each structure are
each independently selected from: --H, --(C.sub.1-C.sub.12)-alkyl,
13 O--(C.sub.1-C.sub.12)-alkyl, --(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.6-C.sub.20)-aryl, or -halogen, where the alkyl and aryl
groups are each independently unsubstituted or substituted, where
each substituted --(C.sub.1-C.sub.12)-alkyl group and each
substituted --(C.sub.6-C.sub.20)-aryl group has at least one
substituent and the at least one substituent in each case is
independently selected from --(C.sub.3-C.sub.12)-cycloalkyl,
--(C.sub.3-C.sub.12)-heterocycloalkyl, --(C.sub.6-C.sub.20)-aryl,
fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, where,
in the structures (III), (IV), (V) and (VI), R.sup.23, R.sup.34,
R.sup.45, R.sup.58 are each independently additionally selected
from --O--X with X=protecting group, where the protecting group X
is selected from
--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl, or
--COO--(C.sub.1-C.sub.12)-alkyl.
3. The compound according to claim 1, wherein the heterocyclic
selenaphosphite has the general structure (Ia) ##STR00020## where
R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and
R.sup.9 are each independently selected from: --H,
--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl, --O--(C.sub.6-C.sub.20)-aryl, or
-halogen, and --R.sup.1 in the heterocyclic selenaphosphite of the
general structure (Ia) is independently selected from the
structures (II), (III), (IV), (V), (VI), (VII), (VIII), (IX) and
(X) ##STR00021## ##STR00022## where the radicals R.sup.10,
R.sup.11, R.sup.12, R.sup.13, R.sup.14 in the structure (II),
R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20,
R.sup.21 and R.sup.22 in structure (III), R.sup.24, R.sup.25,
R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31,
R.sup.32 and R.sup.33 in structure (IV), R.sup.35, R.sup.36,
R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41, R.sup.42,
R.sup.43 and R.sup.44 in structure V, R.sup.46, R.sup.47, R.sup.48,
R.sup.49, R.sup.50, R.sup.51, R.sup.52, R.sup.53, R.sup.54,
R.sup.55, R.sup.56 and R.sup.57 in structure (VI), R.sup.59,
R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64 and R.sup.65 in
structure (VII), and R.sup.66, R.sup.67, R.sup.68, R.sup.69,
R.sup.70, R.sup.71, R.sup.72, R.sup.73 and R.sup.74 in structure
(VIII), in each structure are each independently selected from:
--H, --(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.1-C.sub.12)-alkyl, or
-halogen, and where, in each case independently, in addition to the
aforementioned groups in the structures (III), (IV), (V) and (VI),
R.sup.23, R.sup.34, R.sup.45, R.sup.58 are each independently
selected from --H, --(C.sub.1-C.sub.12)-alkyl, -halogen and --O--X
with X=protecting group, where the protecting group X is selected
from --(C.sub.1-C.sub.12)-alkyl,
--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl, or
--COO--(C.sub.1-C.sub.12)-alkyl.
4. The compound according to claim 3, wherein the heterocyclic
selenaphosphite of the general structure (Ia) is selected from a
compound of structure (Ib) with R.sup.1 corresponding to the
definition immediately above ##STR00023## where R.sup.2, R.sup.4,
R.sup.7 and R.sup.9 are each independently selected from:
--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl, --O--(C.sub.6-C.sub.20)-aryl, or
-halogen, where the alkyl groups are each independently linear,
branched or cyclic.
5. The compound according to claim 1, wherein in the heterocyclic
selenaphosphite of the general structure (I) R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each
independently selected from: --H, --(C.sub.1-C.sub.12)-alkyl, or
--O--(C.sub.1-C.sub.12)-alkyl, and --R.sup.1 in the heterocyclic
selenaphosphite of the general structure (I) is independently
selected from the structures (II), (III), (IV), (V), (VI), (VII),
(VIII), (IX) and (X): ##STR00024## ##STR00025## where the radicals
R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14 in the structure
(II), R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20,
R.sup.21 and R.sup.22 in structure (III), R.sup.24, R.sup.25,
R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31,
R.sup.32 and R.sup.33 in structure (IV), R.sup.35, R.sup.36,
R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41, R.sup.42,
R.sup.43 and R.sup.44 in structure (V), R.sup.46, R.sup.47,
R.sup.48, R.sup.49, R.sup.50, R.sup.51, R.sup.52, R.sup.53,
R.sup.54, R.sup.55, R.sup.56 and R.sup.57 in structure (VI),
R.sup.59, R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64 and
R.sup.65 in structure (VII), and R.sup.66, R.sup.67, R.sup.68,
R.sup.69, R.sup.70, R.sup.71, R.sup.72, R.sup.73 and R.sup.74 in
structure (VIII), in each structure are each independently selected
from: --H, --(C.sub.1-C.sub.12)-alkyl, or
--O--(C.sub.1-C.sub.12)-alkyl, and where in each case
independently, in addition to the aforementioned groups in the
structures (III), (IV), (V) and (VI), R.sup.23, R.sup.34, R.sup.45,
R.sup.58 are each independently selected from --H and --O--X with
X=protecting group, where the protecting group X is selected from
--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl, or
--COO--(C.sub.1-C.sub.12)-alkyl.
6. A rhodium hydroformylation catalyst comprising: the compound
according to claim 1.
7. A process for preparing at least one heterocyclic
selenaphosphite of the general structure (I) ##STR00026## where
R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and
R.sup.9 are each independently selected from: --H,
--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl, --O--(C.sub.6-C.sub.20)-aryl, -halogen,
--OC.dbd.O--(C.sub.1-C.sub.12)-alkyl, --S-alkyl, --S-aryl,
--COO--(C.sub.1-C.sub.12)-alkyl, --CONH--(C.sub.1-C.sub.12)-alkyl,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --SO.sub.3H, --CN, or --N[(C.sub.1-C.sub.12)-alkyl].sub.2,
where the alkyl groups are each independently linear, brandied or
cyclic, Where the alkyl and aryl groups are each independently
unsubstituted cr substituted, where each substituted
--(C.sub.1-C.sub.12)-alkyl group and substituted
--(C.sub.6-C.sub.20)-aryl group has at least, one substituent and
the at least one substituent in each case is independently selected
from --(C.sub.3-C.sub.12)-cycloalkyl,
--(C.sub.3-C.sub.12)-heterocycloalkyl, --(C.sub.6-C.sub.20)-aryl,
fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, and
where --R.sup.1 is independently selected from
--O--(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.6-C.sub.20-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.6-C.sub.20)-aryl-O--(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)- alkyl,
--O--(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, or
--O--(C.sub.3-C.sub.12)-cycloalkyl, where alkyl in each case is
independently linear, branched or cyclic, where the alkyl and aryl
groups mentioned are each independently unsubstituted or
substituted, each substituted --(C.sub.6-C.sub.20)-aryl group has
at least one or more than one substituent; and where the
substituents on each aryl group are independently selected from:
--O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.3-C.sub.12,)-cycloalkyl,
--(C.sub.3-C.sub.12)heterocycloalkyl, --(C.sub.6-C.sub.20)-aryl,
cyano, -halogen, --O--COO--(C.sub.1-C.sub.12)-alkyl, or
--N[(C.sub.1-C.sub.12)-alkyl].sub.2, comprising at least the
process step of (i) reacting a selenodiaryl of the general
structure (XI) ##STR00027## where R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each
independently selected from: --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.6-C.sub.20)-aryl, -halogen,
--OC.dbd.O--(C.sub.1-C.sub.12)-alkyl, --S-alkyl, --S-aryl,
--COO--(C.sub.1-C.sub.12)-alkyl, --CONH--(C.sub.1-C.sub.12)-alkyl,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --SO.sub.3H, --CN, or --N[(C.sub.1-C.sub.12)-alkyl].sub.2,
where the alkyl groups are each independently linear, branched or
cyclic, where the alkyl and aryl groups are each independently
unsubstituted or substituted, where each substituted
--(C.sub.1-C.sub.12)-alkyl group and substituted
--(C.sub.6-C.sub.20)-aryl group has at least one substituent and
the at least one substituent in each case is independently selected
from --(C.sub.3-C.sub.12)-cycloalkyl,
--(C.sub.3-C.sub.12)-heterocycloalkyl, --(C.sub.6-C.sub.20)-aryl,
fluorine, chlorine, cyano, formyl, acyl or alkoxyearbonyl, (ii)
with a dihalophosphite compound R.sup.1P(Hal).sub.2, where Hal is
selected from fluorine, chlorine, bromine, or iodine, where R.sup.1
corresponds to the definition immediately above, (iii) and
obtaining at least one selenaphosphite of the general structure
(I).
8. The process according to claim 7, wherein the selenodiaryl of
the general structure (XI) corresponds to a compound of the
structure (XIa) ##STR00028## where R.sup.2, R.sup.4, R.sup.7 and
R.sup.9 are each independently selected from:
--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl, --O--(C.sub.6-C.sub.20)-aryl, or
-halogen, where the alkyl groups are each independently linear,
branched or cyclic.
9. The process according to claim 7, wherein in the dihalophosphite
compound R.sup.1P(Hal).sub.2 Hal is selected from fluorine,
chlorine, bromine, or iodine, and R.sup.1 is independently selected
from the structures (II), (III), (IV), (V), (VI), (VII), (VIII),
(IX) and (X) ##STR00029## ##STR00030## where the radicals R.sup.10,
R.sup.11, R.sup.12, R.sup.13, R.sup.14 in the structure (II),
R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20,
R.sup.21 and R.sup.22 in structure (III), R.sup.24, R.sup.25,
R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31,
R.sup.32 and R.sup.33 in structure (IV), R.sup.35, R.sup.36,
R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41, R.sup.42,
R.sup.43 and R.sup.44 in structure (V), R.sup.46, R.sup.47,
R.sup.48, R.sup.49, R.sup.50, R.sup.51, R.sup.52, R.sup.53,
R.sup.54, R.sup.55, R.sup.56 and R.sup.57 in structure (VI),
R.sup.59, R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64 and
R.sup.65 in structure (VII), and R.sup.66, R.sup.67, R.sup.68,
R.sup.69, R.sup.70, R.sup.71, R.sup.72, R.sup.73 and R.sup.74 in
structure (VIII), are each independently selected from: --H,
--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.1-C.sub.12)-alkyl, or
-halogen, and where, in each case independently, in addition to the
aforementioned groups in the structures (III), (IV), (V) and (VI),
R.sup.23, R.sup.34, R.sup.45, R.sup.58 are each independently
selected from --H, --(C.sub.1-C.sub.12)-alkyl, -halogen and --O--X
with X=protecting group, where the protecting group X is selected
from --(C.sub.1-C.sub.12)-alkyl,
--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl, or
--COO--(C.sub.1-C.sub.12)-alkyl.
10. The process according to claim 7, wherein (i) the reaction is
effected in the presence of a base.
11. The process according to claim 7, wherein the selenodiaryl of
the general structure (XI) is reacted with R.sup.1P(Hal).sub.2 in a
molar ratio of 10:1 to 1:10.
12. The process according to claim 7, wherein R.sup.1P(Hal).sub.2
is R.sup.1PCl.sub.2 or R.sup.1PBr.sub.2.
13. The process according to claim 7, wherein (i) the reaction is
effected in a temperature range from -45 to 80.degree. C.
14. The process of claim 10, wherein (i) the reaction is effected
in the presence of an amine base or pyridine base.
15. The process of claim 10, wherein (i) the reaction is effected
in the presence of an alkylamine.
16. The process of claim 11, wherein the selenodiaryl of the
general structure (XI) is reacted with R.sup.1P(Hal).sub.2 in a
molar ratio of 2:1 to 1:2.
17. The process of claim 13, wherein (i) the reaction is effected
in the temperature range from -15 to 30.degree. C.
Description
Novel heterocyclic selenaphosphites, process for preparation
thereof and use thereof as ligand for employment in complexes.
T. K. Paine describes a synthesis of
2,2'-selenobis(4,6-di-tert-butylphenol) using selenium dioxide. The
preparation of 2,2'-selenobis(4,6-di-tert-butylphenol) is effected
here in an acidic medium with addition of concentrated hydrochloric
acid, The product is obtained with a yield of 25% (T. K. Paine et
al., "Manganese complexes of mixed O, X, O-donor ligands (X=S or
Se): synthesis, characterization and catalytic reactivity", Dalton
Trans., 2003, 15, 3136-3144). It is particularly disadvantageous
here that the yields are very low and therefore in need of
improvement.
H. M. Lin et al., "A novel and efficient synthesis of selenides",
ARKIVOC, 2012, viii, 146-156, discloses another multi-stage
synthetic route using Grignard reagents. A synthetic route to
selenobiaryl ethers is disclosed in which bromine must be added to
the corresponding phenol in order to then convert the product to a
Grignard reagent with magnesium. The Grignard reagent can then
react with the added selenium before the actual coupling to give
the biaryl ether:
##STR00001##
The product was obtained in a good yield, but this synthetic route
is very complex, which makes it unattractive for industrial scale
use. In this case, a multitude of synthetic steps are needed, the
procedure for which is not uncritical in some cases, especially
considering scale-up and using standards which are customary in
industry. Moreover, this synthetic route gives rise to large
amounts of waste products and solvents which have to be disposed of
in a costly and inconvenient manner, one reason for which is the
use of bromine.
EP 15168645.8 or U.S. Ser. No. 14/720,063 describes a large-scale
economic synthetic route for preparing selenodiphenols.
The reactions between olefin compounds, carbon monoxide and
hydrogen in the presence of a catalyst to give the aldehydes
comprising one additional carbon atom are known as hydroformylation
or oxidation. In these reactions, compounds of the transition
metals of group VIII of the Periodic Table of the Elements are
frequently employed as catalysts. Known ligands are, for example,
compounds from the classes of the phosphines, phosphites and
phosphonites, each with trivalent phosphorus P.sup.III. A good
overview of the status of hydroformylation of olefins is found in
R. Franke, D. Selent, A. Borner, "Applied Hydroformylation", Chem.
Rev., 2012, DOI:10.1021/cr3001803.
Every catalytically active composition has its specific benefits.
According to the feedstock and target product, therefore, different
catalytically active compositions are used.
Rhodium-monophosphite complexes in catalytically active
compositions are suitable for the hydroformylation of branched
olefins having internal double bonds. Since the 1970s, there have
been descriptions of the use of "bulky phosphites" in
hydroformylation (see, inter alfa, van Leeuwen et al., Journal of
Catalysis, 2013, 298, 198-205). These feature good activity, but
the n/i selectivity for terminally oxidized compounds is low and in
need of improvement.
In these hydroformylations, monophosphites and bisphosphites are
generally used, which are often formed from biphenol units. The
development of novel ligands is frequently limited by the available
biphenol, that is, ligand units. For instance, 2,2'-selenobiaryl
ethers and also diphenyiseienoxides and diphenylselenides represent
a highly interesting class of compound. The 2,2'-selenobiaryl
ethers are currently only being used in certain complexes,
especially those containing manganese, but they have great
potential for further uses.
The object of the invention was to provide a further wholly novel
substance class of ligands and ligand units in order to broaden the
field of available ligands for the respective specific complexes in
catalysis. The object also consisted of producing ligands for
rhodium hydroformylation catalysts. The object therefore also
consisted of novel intermediates as ligand units for preparing
ligands. The objects are achieved with the heterocyclic
selenaphosphites according to claim 1, the process according to
claim 6 and the use according to claim 14. Particular embodiments
are disclosed in the dependent claims and also detailed in the
description. The objects are preferably achieved by
selenaphosphites of the structures I and Ia, especially with
R.sup.1 selected from structure I, VII, VIII, IX and X. In the
structures, the hydrogen-, alkyl- and
--O--(C.sub.1-C.sub.12)-alkyl-substituted compounds of R.sup.1 in
the structures mentioned are particularly preferred compounds.
The invention provides compounds of a heterocyclic selenaphosphite
having a general structure I
##STR00002##
where R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8
and R.sup.9 are each independently selected from: --H,
--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl, --O--(C.sub.6-C.sub.20)-aryl, -halogen,
--OC.dbd.O--(C.sub.1-C.sub.12)-alkyl, --S-alkyl, --S-aryl,
--COO--(C.sub.1-C-.sub.12)-alkyl, --CONH--(C.sub.1-C.sub.12)-akyl,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --SO.sub.3H, --CN, --N[(C.sub.1-C.sub.12)-alkyl].sub.2,
where the alkyl and aryl groups are each independently
unsubstituted or substituted, where each substituted
-(C.sub.1-C.sub.12)-alkyl group and substituted
-(C.sub.6-C.sub.20)-aryl group may have at least one substituent
and the at least one substituent in each case is independently
selected from -(C.sub.3-C.sub.12)-cycloalkyl,
-(C.sub.3-C.sub.12)-heterocycloalkyl, -(C.sub.6-C.sub.20)-aryl,
fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, and
where --R.sup.1 is independently selected from
--O--(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.6-C.sub.20)-aryl-O--(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.3-0.sub.12)-cyclcalkyl,
where alkyl in each case is independently linear, branched or
cyclic, where the alkyl and aryl groups mentioned are each
independently unsubstituted or substituted, each substituted
--(C.sub.6-C.sub.20)-aryl group has at least one or more than one
substituent;
where the substituents on each aryl group may independently be
selected from: --O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.3-C.sub.12)-cycloalkyl,
--(C.sub.3-C.sub.12)-heterocycloalkyl, --(C.sub.6-C.sub.20)-aryl,
cyano, -halogen, --O(C.dbd.O)--O--(C.sub.1-C.sub.12)-alkyl,
--N[(C.sub.1-C.sub.12)-alkyl].sub.2.
In particularly preferred alternatives, R.sup.1 in the structure I
may be selected from compounds of the structures II, III, IV, V,
VI, VII, VIII, IX and X which follow. R.sup.1 in the structure I is
an --O-bridged organofunctional radical. IX is a cyclododecanyl
radical and X a menthyl radical.
##STR00003## ##STR00004##
where the radicals
R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14 in the structure
II,
R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20,
R.sup.21, R.sup.22 and R.sup.23 in structure III,
R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29,
R.sup.30, R.sup.31, R.sup.32, R.sup.33 and R.sup.34 in structure
IV,
R.sup.35, R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40,
R.sup.41, R.sup.42, R.sup.43, R.sup.44 and R.sup.45 in structure
V,
R.sup.46, R.sup.47, R.sup.48, R.sup.49, R.sup.50, R.sup.51,
R.sup.52, R.sup.53, R.sup.54, R.sup.55, R.sup.56, R.sup.57 and
R.sup.58 in structure VI,
R.sup.59, R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64 and
R.sup.65 in structure VII, and
R.sup.66, R.sup.67, R.sup.68, R.sup.69, R.sup.70, R.sup.71,
R.sup.72, R.sup.73 and R.sup.74 in structure VIII,
in each structure may each independently be selected from: --H,
--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl, --O--(C.sub.6-C.sub.20)-aryl, -halogen,
where the alkyl and aryl groups may each independently be
unsubstituted or substituted, where each substituted
--(C.sub.1-C.sub.12)-alkyl group and each substituted
--(C.sub.6-C.sub.20)-aryl group may have at least one substituent
and the at least one substituent may in each case independently be
selected from --(C.sub.3-C.sub.12)-cycloalkyl,
--(C.sub.3-C.sub.12)-heterocycloalkyl, --(C.sub.6-C.sub.20)-aryl,
fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl,
where, in the structures III, IV, V and VI, R.sup.23, R.sup.34,
R.sup.45, R.sup.58 may each independently additionally be selected
from --O--X with X=protecting group, where the protecting group X
may be selected from --(C1-C12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--COO--(C.sub.1-C.sub.12)-alkyl.
In a further particularly preferred alternative, the heterocyclic
selenaphosphite may have the general structure Ia
##STR00005##
where each of R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7,
R.sup.8 and R.sup.9 in the structure Ia is independently selected
from: --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.6-C.sub.20)-aryl, -halogen, and with --R.sup.1 in the
heterocyclic selenaphosphite of the general structure Ia
independently selected from the structures II, III, IV, V, VI, VII,
VIII, IX and X, as illustrated above, where the radicals R.sup.10,
R.sup.11, R.sup.12, R.sup.13, R.sup.14 in the structure II,
R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20,
R.sup.21 and R.sup.22 in structure III, R.sup.24, R.sup.25,
R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31,
R.sup.32 and R.sup.33 in structure IV, R.sup.35, R.sup.36,
R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41, R.sup.42,
R.sup.43 and R.sup.44 in structure V, and/or R.sup.46, R.sup.47,
R.sup.48, R.sup.49, R.sup.50, R.sup.51, R.sup.52, R.sup.53,
R.sup.54, R.sup.55, R.sup.56 and R.sup.57 in structure VI,
R.sup.59, R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64 and
R.sup.65 in structure VII, and R.sup.66, R.sup.67, R.sup.68,
R.sup.69, R.sup.70, R.sup.71, R.sup.72, R.sup.73 and R.sup.74 in
structure VIII, may each independently be selected from: --H,
--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.1-C.sub.12)-alkyl,
-halogen, and where, in each case independently, in addition to the
aforementioned groups in the structures III, IV, V and VI,
R.sup.23, R.sup.34, R.sup.45, R.sup.58 may each independently be
selected from --H, -(C.sub.1-C.sub.12)-alkyl, -halogen and --O--X
with X=protecting group, where the protecting group X is selected
from -(C.sub.1-C.sub.12)-alkyl,
--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--COO--(C.sub.1-C.sub.12)-alkyl,
In accordance with a further preferred alternative, the
heterocyclic selenaphosphite of the general structure la may be
selected from at least one compound of the structure Ib with
R.sup.1 corresponding to the definition for the compound of the
structure Ia,
##STR00006##
where R.sup.2, R.sup.4, R.sup.7 and R.sup.9 may each be
independently selected from: --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.6-C.sub.20)-aryl, halogen.
The invention likewise provides the aforementioned structures of
the selenaphosphites and selenodiaryls of the structures I and Ia
with R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8
and R.sup.9, each of which may independently selected from: --H,
--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-aryl,
--(C.sub.6-C.sub.20)-aryl,--O--(C.sub.6-C.sub.20)-aryl, -halogen,
wherein the alkyl and aryl groups are each independently
unsubstituted. The alkyl groups are preferably unsubstituted. More
preferably, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7,
R.sup.8 and R.sup.9 are each independently selected from methyl,
ethyl, tert-butyl, isopentyl, methoxy.
The invention likewise provides the aforementioned structures of
the selenaphosphites and selenodiaryls of the structures Ib with
R.sup.2, R.sup.4, R.sup.7 and R.sup.9, each of which may
independently selected from: --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.6-C.sub.20)-aryl, -halogen, wherein the alkyl and aryl
groups are each independently unsubstituted.
In an alternative, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7, R.sup.8 and R.sup.9 in a heterocyclic selenaphosphite of
the general structure I and Ia are each independently selected
from: --H and --(C.sub.1-C.sub.12)-alkyl and/or
--O--(C.sub.1-C.sub.12)-alkyl groups, wherein the alkyl groups may
be linear, branched or cyclic. The alkyl groups are preferably
unsubstituted.
In an alternative, R.sup.2, R.sup.4, R.sup.7 and R.sup.9 in a
heterocyclic selenaphosphite of the general structure Ib are each
independently selected from:
--(C.sub.1-C.sub.12)-alkyl and/or --O--(C.sub.1-C.sub.12)-alkyi
groups, where the alkyl groups may be linear, branched or cyclic.
The alkyl groups are preferably unsubstituted. Particular
preference is given to R.sup.2, R.sup.4, R.sup.7, R.sup.9, each of
which may be methyl, ethyl, tert-butyl, isopentyl, methoxy.
For the heterocyclic selenaphosphites of the aforementioned general
structure Ia or Ib, it is further preferred when R.sup.1 may
correspond to one of the structures selected from II, III, IV, V,
VI, VIII, IX and X, particular preference being given to the
structures II, III, and radicals in the structures being selected
from:
R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14 in the structure
II,
R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20,
R.sup.21, R.sup.22 and R.sup.23 in structure III,
R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29,
R.sup.30, R.sup.31, R.sup.32, R.sup.33 and R.sup.34 in structure
IV,
R.sup.35, R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40,
R.sup.41, R.sup.42, R.sup.43, R.sup.44 and R.sup.45 in structure V,
and/or
R.sup.46, R.sup.47, R.sup.48, R.sup.49, R.sup.50, R.sup.51,
R.sup.52, R.sup.53, R.sup.54, R.sup.55, R.sup.56, R.sup.57 and
R.sup.58 in structure VI,
R.sup.59, R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64 and
R.sup.65 in structure VII, and
R.sup.66, R.sup.67, R.sup.68, R.sup.69, R.sup.70, R.sup.71,
R.sup.72, R.sup.73 and R.sup.74 in structure VIII,
in each structure may each independently be selected from: --H,
--(C.sub.1-C.sub.12)-alkyl, -halogen, where the alkyl groups may
each independently be substituted,
where, in the structures III, IV, V and VI, R.sup.23, R.sup.34,
R.sup.45, R.sup.58 may each independently be selected from --H,
--(C.sub.1-C.sub.12)-alkyl, --O--X with X=protecting group, where
the protecting group X may be selected from
--(C.sub.1-C.sub.12)-akyl,
--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--COO--(C.sub.1-C.sub.12)-alkyl.
In structure II, R.sup.10 and R.sup.12 are preferably selected from
tert-butyl, methyl, ethyl, isopropyl, isopentyl, and R.sup.11 ,
R.sup.13, R.sup.14 are --H.
Likewise claimed is at least one heterocyclic selenaphosphite of
the general structure I, where R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each independently
selected from: --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, and --R.sup.1 in the heterocyclic
selenaphosphite of the general structure I is independently
selected from the structures II, III, IV, V, VI, VII, VIII, IX and
X, where the aforementioned radicals are each independently
selected from: --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, and where, in each case
independently, in addition to the aforementioned radicals in the
structures III, IV, V and VI, R.sup.23,R.sup.34, R.sup.45,
R.sup.58are each independently selected from --H,
--(C.sub.1-C.sub.12)-alkyl, and --O--X with X=protecting group,
where the protecting group X is selected from
--(C.sub.1-C.sub.12)-alkyl, --(C.sup.6C.sub.20)-aryl,
--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.2)-aryl-O--(C.sub.1-C.sub.12)-alkyl.
Likewise claimed is at least one heterocyclic selenaphosphite of
the general structure I, where R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each independently
selected from: --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1.sup.-C.sub.12)-alkyl, and --R.sup.1 in the
heterocyclic selenaphosphite of the general structure I is
independently selected from the structures II, VII, VIII, where the
radicals in II, VII, VIII are each independently selected from:
--H, --(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.1-C.sub.12)-alkyl.
Likewise claimed is at least one heterocyclic selenaphosphite of
the general structure I, where R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each independently
selected from: --H, --(C.sub.1.-C.sub.12)-alkyl, and --R.sup.1 in
the heterocyclic selenaphosphite of the general structure I is
independently selected from the structure II, where the radicals in
II are each independently selected from: --H,
--(C.sub.1-C.sub.12)-alkyl.
Likewise claimed is at least one heterocyclic selenaphosphite of
the general structure I, where R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each independently
selected from: --H, --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, and --R.sup.1 in the heterocyclic
selenaphosphite of the general structure I is independently
selected from the structures IX and X.
Particular preference is given to a heterocyclic selenaphosphite of
the general structure Ib where R.sup.2, R.sup.4, R.sup.7 and
R.sup.8 are each methyl and --R.sup.1 corresponds to the
single-crystal structure H with R.sup.10, R.sup.12=methyl and
R.sup.11, R.sup.13 and R.sup.14=--H.
The invention further provides a process for preparing at least one
heterocyclic selenaphosphite of the general structure I according
to the above definition, and the selenaphosphites obtainable by the
process.
##STR00007##
where R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8
and R.sup.9 are each independently selected from: --H,
--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl, --O--(C.sub.6-C.sub.20)-aryl, -halogen,
--OC.dbd.O--(C.sub.1-C.sub.12)-alkyl, --S-alkyl, --S-aryl,
--COO--(C.sub.1-C.sub.12)-alkyl,--CONH--(C.sub.1-C.sub.12)-alkyl,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --SO.sub.3H, --CN, --N[(C.sub.1-C.sub.12)-alkyl].sub.2,
where the alkyl and aryl groups are each independently
unsubstituted or substituted, where the respective substituted
--(C.sub.1-C.sub.12)-alkyl group and substituted
--(C.sub.6-C.sub.20)-aryl group has at least one substituent and
the at least one substituent in each case is independently selected
from --(C.sub.3-C.sub.2)-cycloalkyl,
--(C.sub.3-C.sub.12)-heterocycloalkyl, --(C.sub.6-C.sub.20)-aryl,
fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, and
where --R.sup.1 may independently be selected from
--O--(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.6-C.sub.20)-aryl-O--(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl-(C.sub.5-C.sub.20)-aryl,
--O--(C.sub.3-C.sub.12)-cycloalkyl, where alkyl may in each case
independently be linear, branched or cyclic,
where the alkyl and aryl groups mentioned may each independently be
unsubstituted or substituted, each substituted
--(C.sub.6-C.sub.20)-aryl group may have at least one or more than
one substituent;
where the substituents on each aryl group may independently be
selected from: --O --(C.sub.1-C.sub.12)-alkyl,
--(C,.sub.1-C.sub.12)-alkyl-O-(C.sub.1-C.sub.12)-aryl,
--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.3-C.sub.12)-cycloalkyl,
--(C.sub.3-C.sub.12)-heterocycloalkyl, --(C.sub.6-C.sub.20)-aryl,
cyano, -halogen, --OCOO--(C.sub.1-C.sub.12)-alkyl,
--N[(C.sub.1-C.sub.12)-alky].sub.2.
comprising at least the process step of (i) reacting a selenodiaryl
of the general structure XI
##STR00008## where R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7, R.sup.8 and R.sup.9 are each independently selected from:
--H, --(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl, --O--(C.sub.6-C.sub.20)-aryl, -halogen,
--OC.dbd.O--(C.sub.1-C.sub.12)alkyl, --S-alkyl, --S-aryl,
--COO--(C.sub.1-C.sub.12)-alkyl, --CONH--(C.sub.1-C.sub.12)-alkyl,
--CO--(C.sub.1-C.sub.12)-alkyl, --CO--(C.sub.6-C.sub.20)-aryl,
--COOH, --SO.sub.3H, --CN, --N[(C.sub.1-C.sub.12)-alkyl].sub.2,
where the alkyl and aryl groups are each independently
unsubstituted or substituted, where each substituted
--(C.sub.1-C.sub.12)-alkyl group and substituted
--(C.sub.6-C.sub.20)-aryl group may have at least one substituent
and the at least one substituent in each case is independently
selected from -(C.sub.3-0.sub.12)-cycloalkyl,
--(C.sub.3-C.sub.12)-heterocycloalkyl, --(C.sub.6-C.sub.20)-aryl,
fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl,
especially as defined above for structure I, (ii) with a
dihalophosphite compound R.sup.1P(Hal).sub.2 of the formula XII
where Hal is selected from fluorine, chlorine, bromine, iodine,
preference being given to chlorine and bromine, particular
preference to chlorine, where R.sup.1 may correspond to the
aforementioned definition, particular preference being given to
reaction with a compound of the formula XII selected from
R.sup.1PCl.sub.2 and R.sup.1PBr.sub.2, (iii) and obtaining at least
one selenaphosphite of the general structure I.
In accordance with a preferred embodiment of the process, it is
possible to use a selenodiaryl of the general structure XIa
##STR00009##
where R.sup.2, R.sup.4, R.sup.7 and R.sup.9 are each independently
selected from: --(C.sub.1-C.sub.12)-alkyl,
--O--(C.sub.1-C.sub.12)-alkyl, --(C.sub.6-C.sub.20)-aryl,
--O--(C.sub.5-C.sub.20)-aryl, -halogen.
In addition, it is preferable when, in the process, the compound
reacted with the selenodiaryl of the structure XI or XIa is a
dihalophosphite compound of the formula R.sup.1P(Hal).sub.2 of the
formula XII with Hal selected from fluorine, chlorine, bromine,
iodine, especially chlorine and bromine, particular preference
being given to chlorine, in which R.sup.1 may independently be
selected from the structures II, III, IV, V, VI, VII, VIII, IX and
X as defined above, where the radicals
R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14 in the structure
II,
R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20,
R.sup.21 and R.sup.22 in structure III,
R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29,
R.sup.30, R.sup.31, R.sup.32 and R.sup.33 in structure IV,
R.sup.35, R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40,
R.sup.41, R.sup.42, R.sup.43 and R.sup.44 in structure V,
R.sup.46, R.sup.47, R.sup.48, R.sup.49, R.sup.50, R.sup.51,
R.sup.52, R.sup.53, R.sup.54, R.sup.55, R.sup.56 and R.sup.57 in
structure VI,
R.sup.59, R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64 and
R.sup.65 in structure VII, and
R.sup.66, R.sup.67, R.sup.68, R.sup.69, R.sup.70, R.sup.71,
R.sup.72, R.sup.73 and R.sup.74 in structure VIII,
in each structure are each independently selected from: --H,
--(C.sub.1-C.sub.12)-alkyl, --O--(C.sub.1-C.sub.12)-alkyl,
-halogen, and where, in each case independently, in addition to the
aforementioned groups in the structures III, IV, V and VI,
R.sup.23, R.sup.34, R.sup.45, R.sup.56 are each independently
selected from --H, --(C.sub.1-C.sub.12)-alkyl, -halogen and --O--X
with X=protecting group, where the protecting group X is selected
from --(C.sub.1-C.sub.12)-alkyl,
--(C.sub.1-C.sub.12)-alkyl-O--(C.sub.1-C.sub.12)-alkyl,
--(C.sub.6-C.sub.20)-aryl-O--(C.sub.1-C.sub.12)-alkyl,
--COO-(C.sub.1-C.sub.12)-alkyl.
According to the invention, the dihalophosphite compound
R.sup.1P(Hal).sub.2 is an organofunctional dihalophosphite
compound.
The (i) reaction in the process according to the invention is
effected in the presence of a base, especially of an amine or a
pyridine base, especially an alkylamine such as triethylamine or
dimethylaminobutane, especially triethylamine.
In addition, the (i) reaction is effected by reacting the
selenodiaryl of the general structure XI with R.sup.1P(Hal).sub.2
of the formula XII in a molar ratio of 10:1 to 1:10, preferably in
a ratio of 2:1 to 1:2, more preferably 1.5:1 to 1:1.5.
In addition, the (i) reaction is preferably effected at a
temperature of --45 to 80.degree. C., particularly of -15 to
30.degree. C., especially of -5 to 5.degree. C.
The invention likewise provides for the use of a heterocyclic
selenaphosphite of the structure I, Ia and Ib or of the composition
comprising at least one selenaphosphite of the structure I
obtainable by the process as ligand.
The terms "phenol", "aryl" and "phosphite" are used as generic
terms in this application and therefore also encompass substituted
structures of the compounds mentioned.
One or more substituents in the aforementioned structures of the
selenaphosphites and selenodiaryls comprise preferably 1 to 10
substituents, in particular 1 to 3.
In the context of the invention, the expression
"-(C.sub.1-C.sub.12)-alkyl" encompasses straight-chain and branched
alkyl groups. Preferably, these groups are unsubstituted
straight-chain or branched --(C.sub.1-C.sub.8)-alkyl groups and
most preferably
--(C.sub.1-C.sub.6)-alkyl groups. Examples of
--(C.sub.1-C.sub.12)-alkyl groups are particularly methyl, ethyl,
propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,
n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl,
1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl,
1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl,
4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,
2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl,
3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,
1-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl,
2-ethylpentyl, 1-propylbutyl, n-octyl, 2-ethylhexyl,
2-propylheptyl, nonyl, decyl.
Halogen as substituent on alkyl or aryl includes fluorine,
chlorine, bromine and iodine, particular preference being given to
chlorine and fluorine.
All elucidations relating to the expression
--(C.sub.1-C.sub.12)-alkyl in the aforementioned structures of the
selenaphosphites and selenodiaryls according to the invention also
apply to the alkyl groups in --O--(C.sub.1-C.sub.12)-alkyl, that
is, in --(C.sub.1-C.sub.12)-alkoxy.
25
Preference is given to unsubstituted straight-chain or branched
--(C.sub.1-C.sub.6)-alkoxy groups,
Substituted --(C.sub.1-C.sub.12)-alkyl groups and substituted
--(C.sub.1-C.sub.12)-alkoxy groups in the aforementioned structures
of the selenaphosphites and selenodiaryls may have one or more
substituents, depending on their chain length. The substituents are
preferably each independently selected from:
--(C.sub.3-C.sub.12)-cycloalkyl,
--(C.sub.3-C.sub.12)-heterocycloalkyl, --(C.sub.6-C.sub.20)-aryl,
fluorine, chlorine, cyano, formyl, acyl orzr alkoxycarbonyl. This
definition applies to all substituted alkyl or alkoxy groups of the
present invention.
All elucidations relating to the expression
--(C.sub.6-C.sub.20)-aryl in the aforementioned structures of the
selenaphosphites and seienodiaryis according to the invention also
apply to the aryl groups in --O--(C.sub.6-C.sub.20)-aryl.
Preference is given to unsubstituted --O--(C.sub.6-C.sub.20)-
groups.
In the context of the present invention, the expression
"--(C.sub.6-C.sub.20)-aryl and
-(C.sub.6-C.sub.20)-aryl-(C.sub.6-C.sub.20)-aryl-" encompasses
mono- or polycyclic aromatic hydrocarbyl radicals. These have 6 to
20 ring atoms, more preferably 6 to 14 ring atoms, especially 6 to
10 ring atoms. Aryl is preferably --(C.sub.6-C.sub.10)-aryl and
--(C.sub.6-C.sub.10)-aryl-(C.sub.8-C.sub.10)-aryl-. Aryl is
especially phenyl, naphthyl, indenyl, fluorenyl, anthracenyl,
phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, coronenyl. More
particularly, aryl is phenyl, naphthyl and anthracenyl.
The expression "--(C.sub.3-C.sub.12)-cycloalkyl", in the context of
the present invention, encompasses mono-, bi- or tricyclic
hydrocarbyl radicals having 3 to 12, especially 5 to 12, carbon
atoms. These include cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclopentadecyl,
norbornyl or adamantyl.
One example of a substituted cycloalkyl would be menthyl.
The expression "--(C.sub.3-C.sub.12)-heterocycloalkyl groups", in
the context of the present invention, encompasses nonaromatic,
saturated or partly unsaturated cycloaliphatic groups having 3 to
12, especially 5 to 12, carbon atoms. The
--(C.sub.3-C.sub.12)-heterocycloalkyl groups have preferably 3 to
8, more preferably 5 or 6, ring atoms. In the heterocycloalkyl
groups, as opposed to the cycloalkyl groups, 1, 2, 3 or 4 of the
ring carbon atoms are replaced by heteroatoms or
heteroatom-containing groups. The heteroatoms or the
heteroatom-containing groups are preferably selected from --O--,
--S--, --N--, --N(.dbd.O)--, --C(.dbd.O)-- or --S(.dbd.O)--,
Examples of --(C.sub.3-C.sub.12)-heterocycloalkyl groups are
tetrahydrothiophenyl, tetrahydrofuryl, tetrahydropyranyl and
dioxanyl.
The invention is further illustrated in detail below by examples
without the invention being limited to the working examples.
General Methods
Solvents and Reagents
All reactions with moisture- and/or oxygen-sensitive substances
were carried out in baked-out apparatuses under an argon
atmosphere. Solvents for extraction and column chromatography were
used at the following purities: dichloromethane (99.9%, Walter,
Cat. No. BIE 073107033) ethyl acetate (99.5%, Walter, Cat. No. BIE
003917025) and n-hexane (95%, Walter (Baker), Cat. No. 8669),
n-heptane (95%, Walter (Baked, Cat. No. 8662). Other solvents for
extraction and column chromatography were of technical quality and
were used without further purification unless otherwise stated. Dry
solvents (abs.) were purified using a Pure Solv MD-7 System and
stored under an argon atmosphere. Benzyl bromide was freshly
distilled (17 mbar/82.degree. C.) prior to use. Deuterated solvents
were distilled from the drying agents specified:
dichloromethane-d.sub.2 (phosphorus pentoxide), toluene-d.sub.8 (1.
KOH; 2. sodium). Chemicals used for the syntheses were supplied by
Sigma Aldrich, Alfa Aesar, Acres Organics, Avantor Performance
Materials B. V., Merck KGaA and ABCR GmbH & Co. KG. These were
used without further purification unless otherwise stated.
Filtration: Filtrations for the removal of resulting solids were
carried out using a G4 frit (pore width: 10-16 .mu.m).
Analysis
IR spectroscopy: IR spectra were recorded with a Nicolet 6700 FT-IR
spectrometer from Thermo Electron. The substances were measured by
ATR methods.
.sup.1H-NMR spectroscopy: .sup.1H-NMR spectra were recorded with a
model AV 300 (300 MHz) and with the model Fourier 300 (300 MHz)
from Bruker, Chemical shifts are stated in units on the
.delta.-scale. The residual proton signals of the solvent
(dichloromethane-d.sub.2: .delta.=5.32 ppm, toluene-d.sub.8:
.delta.=7.09; 7.00; 6.98; 2.09 ppm) served as standard.
.sup.13C-NMR spectroscopy: .sup.13C-NMR spectra were recorded with
models AV 300 (75 MHz) and Fourier 300 (75 MHz) from Bruker. The
signal of the solvent (dichioromethane-d.sub.2: .delta.=54.0 ppm,
toluene-d.sub.8:
.delta.=137.9; 129.2; 128.3; 125.5; 20.4 ppm) served as internal
standard wherein the chemical shifts were taken from the broadband
.sup.1H-decoupled spectra.
.sup.77Se-NMR spectroscopy: .sup.77Se-NMR spectra were recorded
with an AV 300 (57 MHz) from Bruker. The spectra were measured in
broadband .sup.1H-decoupled mode. The chemical shifts are reported
in ppm.
Mass spectrometry: El mass spectra were recorded on a Finnigan MAT
95-XP instrument from Thermo Electron and ESI-TCF mass spectra with
a model 6210 Time-of-Flight LC/MS from Agilent.
SYNTHESIS OF THE PRECURSORS
General Procedure
8.2 mmol of the particular phenol are dissolved in the appropriate
solvent (8.2 m). The reaction mixture is heated, and 4.9 mmol of
selenium dioxide are added while stirring. The solvent is distilled
under reduced pressure (temperature <70.degree. C.), A frit is
prepared with 2.5 cm of silica gel (at the bottom) and 2.5 cm of
zeolite (at the top). The distillation residue is taken up in the
eluent and applied to the filtration column. Cyciohexane:ethyl
acetate (95:5) is used to wash the product off the frit and collect
it in fractions. The fractions containing the product are combined
and freed of the eluent by distillation.
The fractions obtained are recrystallized from 95:5
cyclohexane:ethyl acetate. For this purpose, the solid residue is
dissolved at 50.degree. C., and insoluble residues are filtered off
using a glass frit. The reaction product crystallizes out of the
saturated solution at room temperature overnight. The resulting
crystals are washed once again with cold cyclohexane.
The structural formula shows the main product obtained in each
reaction.
Bis(3,5-dimethyl-2-hydroxyphenyl)selenium; structure XI, 1a
##STR00010##
The reaction is conducted according to the general procedure in a
screw-top test tube. For this purpose, 1.00 g (8.2 mmol, 1.0
equiv.) of
2,4-dimethylphenol and 0.54 g (4.9 mmol, 0.6 equiv.) of selenium
dioxide are dissolved and heated in 1 ml of pyridine. The product
is obtained as a colourless crystalline solid.
.sup.1H-NMR (400 MHz, CDCl.sub.3): .delta. (ppm)=7.12 (s,2H, 6-H),
6.91 (s, 2H, 4-H), 5.97 (s,2H, OH), 2.23 (s, 6H, 3-CH.sub.3) 2.23
(s, 6H, 5-CH.sub.3); .sup.13C-NMR (100 MHz, CDCl.sub.3): .delta.
(ppm)=151.7 (C-2),133.2 (C-3), 133.1 (C-5), 130.4 (C-4), 124.2
(C-6), 114.9 (C-1), 20.3 (5-CH.sub.3), 16.5 (3-CH.sub.3);
.sup.77Se-HMR (76 MHz, CDCl.sub.3): .delta. (ppm)=163.36 ppm.
Bis(3-tert-butly-5-methyl-2-hydroxyphenyl)selenium, structure XI,
1b
##STR00011##
The reaction is conducted according to the general procedure in a
screw-top test tube. For that purpose, 1.32 g (8.0 mmol, 1.0
equiv.) of
2-tert-butyl-4-methylphenol and 0.54 g (4.9 mmol, 0.6 equiv.) of
selenium dioxide were dissolved and heated in 1 ml of pyridine.
.sup.1H-NMR (300 MHz, CDCl.sub.3): .delta. (ppm)=7.15 (s, 2H, 6-H),
7.05 (s, 2H, 4-H), 5.07 (s,2H, OH), 2.21 (s, 6H, 5-CH.sub.3), 2.21
(s, 18H, 3-C(CH.sub.3).sub.3: .sup.13C-NMR (75 MHz, CDCl.sub.3):
.delta. (ppm)=152.1, 136.4, 133.4, 120.1, 129.5, 117.2, 35.1, 29.6,
20.8.
3,3', 5,5'-Tetra-tert-butylbiphenyl-2,2'-diol, structure XI, 1c
##STR00012##
The reaction is conducted according to the general procedure in a
screw-top test tube. For that purpose, 1.67 g (8.2 mmol, 1.0
equiv.) of 2,4-di-tert-butylphenol and 0.55 g (4.9 mmol, 0.6
equiv.) of selenium dioxide were dissolved and heated in 1 ml of
pyridine.
.sup.1H-NMR (400 MHz, CDCl.sub.3): .delta. (ppm)=7.31 (d, J=2.4 Hz,
2H), 7.29 (d, J=2.4), 6.29 (s, 2H), 1.42 (s, 18H), 1.24 (s, 18H);
.sup.13C-NMR (75 MHz, CDCl.sub.3); .delta. (ppm)=151.7, 143.5,
135.8, 129.8, 126.6, 117.2, 35,4, 34.4, 31.6, 29.7.
Biphenols
The biphenols are synthesized analogously to DE102013203865 and
DE102013203867.
Synthesis of the Chlorophosphites
The synthesis of the dichlorophosphites, such as
dichloro((-)-menthyloxy)phosphite, is known to those skilled in the
art and is effected in the manner known per se. Chlorophosphites
can be prepared from the corresponding monohydroxyl compounds by
addition of phosphorus trichloride in the presence of a base. For
further information see also "Phosphorus(III) Ligands in
Homogeneous Catalysis--Design and Synthesis" by Paul C. J. Kamer
and Piet W. N. M. van Leeuwen; John Wiley and Sons, 2012; including
p. 94 ff. and references cited therein.
Synthesis of dichloro(2,4-di-tert-butylphenoxy)phosphite, structure
XII, 2a
##STR00013##
A baked-out 50 ml Schlenk flask under an argon atmosphere was
initially charged with 629 .mu.l (989 mg, 7.20 mmol, 3.6 eq) of
phosphorus trichloride in 20 ml cf abs. n-heptane and cooled to
10.degree. C. In a separate 10 ml Schienk flask, 374 .mu.l (273 mg,
2.70 mmol, 1.35 eq) of triethylamine and 412 mg (2.00 mmol, 1.0 eq)
of 2,4-di-tert-butylphenol were dissolved in 10 ml of n-heptane and
added dropwise to the initial charge of PCl.sub.3 over a period of
90 minutes. The latter was rinsed in with 2.0 ml of abs. n-heptane
and stirred at RT for 19 h. Subsequently, the reaction mixture was
filtered for complete removal of the precipitate formed and the
solids were washed with 10 ml of abs. n-heptane. The solvent of the
pale yellow solution was removed under reduced pressure and the
crude product was dried under vacuum at 50.degree. C. for three
hours. 569 mg (1.86 mmol, 93%, 96% pure) of the title compound 2a
were obtained as colourless oil.
IR (ATR): {circumflex over (v)}(cm.sup.-1)=2958; 2869; 1494; 1398;
1362; 1302; 1210; 1154; 1085; 982; 939; 887; 823; 783; 745; 699;
645; 598; 509; .sup.31P-NMR (122 MHz, Toluene-d.sub.8): .delta.
(ppm)=186.0. MS (El): m/z (%)=306 (10.4)
[C.sub.14H.sub.21Cl.sub.2OP]; 291 (100)
[C.sub.13H.sub.18,Cl.sub.2OP]; 271 (2.06) [C.sub.14H.sub.21ClOP];
HR-MS (El): calc'd for C.sub.14H.sub.21ClOP: 306.07016, found:
306.06994; calc'd for C.sub.14H.sub.21 .sup.37ClOP: 308.06721,
found: 308.06731; C.sub.14H.sub.21Cl.sub.2OP (306.07 g/mol).
Reaction of tert-butyl
(3,3'-di-tert-butyl-2'hydroxy-5,5'-dimethoxy-[1,1'-biphenyl
-2-yl])carbonate with phosphorus trichloride:
##STR00014##
In a 250 ml Schlenk flask which had been repeatedly evacuated and
filled with inert gas, 12 g (0.026 mol) of tert-butyl
(3,3'-di-tert-butyl-2'-hydroxy-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)carbon-
ate were dissolved by stirring in 120 ml of dried toluene and 12.8
ml (0.091 mol) of triethylamine.
In a second 500 ml Schlenk flask, 100 ml of dried toluene were
first stirred together with 8.1 ml (0.091 mol) of phosphorus
trichloride. Subsequently, the phosphorus trichloride-toluene
solution was added dropwise to the previously prepared
carbonate-amine-toluene solution at room temperature within 30
minutes. On completion of addition, the mixture was heated to
80.degree. C. for 30 minutes and cooled to room temperature
overnight. The next morning, the mixture was filtered, the solids
were washed with 50 ml of dried toluene, and the filtrate was
concentrated to dryness. The target product was obtained as a solid
(13.1 g, 89%). .sup.31P-NMR (202.4 MHz, toluene-d.sub.8): 203.2 and
203.3 ppm.
Preparation of biphenyl-3,3',
5,5'-tetra-tert-butyl-2-hydroxy-2'-dichlorophosphite
##STR00015##
In a 250 ml Schlenk flask which had been repeatedly evacuated and
filled with inert gas, 10.62 g (0.025 mol) of
3,3',5,5'-tetra-tert-butyl-2-hydroxy-2'-rnethoxybiphenyl were
dissolved with stirring in 50 ml of dried toluene and admixed with
3.5 ml (0.025 mol) of triethylamine. Added dropwise to the
resulting solution, at room temperature and with vigorous stirring,
are 2.2 ml (0.025 mol) of phosphorus trichloride, and the mixture
is then heated at 105.degree. C. for 4 hours. It is worked up by
filtering off the precipitated ammonium chloride and washing the
filter product 2 times with 25 ml of toluene. The filtrate is
concentrated to dryness. The product was obtained in 63% yield.
Analogously to the preparation of the
dichloro(2,4-di-tert-butylphenoxy)phosphite, it is correspondingly
possible to prepare phenols, 1-naphthols, 2-naphthols, anthracene
derivatives such as 9-hydroxyanthracene, and cycloalkanol
compounds.
The Synthesis of the Selenium Phosphites
Synthesis of 6-(2,4-di-tert-butylphenoxy)-2,4,8,
10-tetramethyldibenzo[d,c][1,3,6,2]dioxaselenapholsphocine,
structure I; 3a
##STR00016##
A baked-out 50 ml Schlenk flask under an argon atmosphere was
initially charged with 191 mg (0.624 mmol, 1.2 eq, 96% pure) of
dichloro(2,4-di-tert-butylphenoxy)phosphite 2a in 5.0 ml of abs.
toluene and cooled to 0.degree. C. In a separate 10 ml Schlenk
vessel, 168 mg (0.522 mmol, 1.0 eg) of selenodiphenol 1a and 159
.mu.l (116 mg, 1.14 mmol, 2.2 eq) of triethylamine were dissolved
in 2.0 ml of abs, toluene. The resulting pale yellow solution was
then added dropwise to the initial charge of dichlorophosphite 2a,
in the course of which the formation of a colourless precipitate
was recorded. The latter was rinsed in with 2.0 ml of abs. toluene
and stirred at RT for 48 h. The reaction mixture was filtered for
complete removal of the precipitate formed, the solids were washed
with 10 ml of abs. toluene, and the solvent was removed under
reduced pressure. After crystallization in 10 ml of abs. n-heptane,
191 mg (0.343 mold, 66%, 99.9% in .sup.31P NMR) of the title
compound 3a were obtained as a colourless solid.
IR (ATR): {circumflex over (v)} (cm.sup.-1)=3425; 2956; 2917; 2865;
1604; 1492; 1464; 1399; 1377; 1360; 1273; 1248; 1208; 1192; 1119;
1084; 1013; 958; 914; 887; 848; 810; 772; 729; 703; 680; 669; 645;
581; 527; 512; 497; 412; .sup.1H-NMR (300 MHz, Toluene-d.sub.8,):
.delta. (ppm)=7.68-7.46 (m, 2H Ar--CH); 7.40-7.31 (m, 2H Ar--CH);
7.05 (dd, J=8.4 Hz, J=2.5 Hz, 1H Ar--CH); 6.64 (ddd, J=2.3 Hz,
J=1.3 Hz, J=0.7 Hz, 2H, Ar--CH); 2.13 (s, 6H, --CH.sub.3);
1.97-1.95 (m, 6H, --CH.sub.3); 1.65 (s, 9H, --C(CH.sub.3).sub.3);
1.31 (s, .sup.9H, --C(CH.sub.3).sub.3); .sup.3C-NMR (75 MHz,
Toluene-d.sub.8);
.delta. (ppm)=152.9 (d, J=5.4 Hz); 150.1 (d, J=4.0 Hz); 145.8;
139.6 (d, J=2.5 Hz); 134.3; 133.8; 133.1; 130.10; 124.4; 124.0;
120.3 (d, J=17.1 Hz); 120.0 (d, J=4.2 Hz); 35.41; 34.57; 31.63;
30.42; 20.16; 17.35; .sup.31P-NMR (122 MHz, Toluene-d.sub.8):
.delta. (ppm)=132.6 (J.sub.P--Se=62.3 Hz); .sup.77Se-NMR (57 MHz,
Toluene-d.sub.8): .delta. (ppm)=323.0 P.sub.Se--P=62.3 Hz);
C.sub.30H.sub.37O.sub.3PSe (556.16 g/mol).
* * * * *